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Introduction
The electronic configuration of CO molecule shows that both
carbon and oxygen atoms has a lone pair of electron. Carbon
atom can donate its electron pair to a transition metal atom
to form OC→M coordinate bond. Hence the compounds form
by combination of CO molecules, with transition metals are
known as metallic carbonyls. Since the electrons supplied
solely by CO molecule in the formation of OC→M bond,
metal atom in carbonyl has zero oxidation state.
Carbonyls have been classified on the basis of the number
of metal atoms present in the carbonyl
i. Mononuclear (or monomeric) carbonyl:
Which is having only one metal atom per molecule and having
type M(CO)y. e.g. V(CO)6, Cr(CO)6 etc.
ii. Polynuclear carbonyl:
Which contain two or more metal atoms per molecule having type
Mx(CO)y. how ever some authors call carbonyls containing two
metal atoms are called bridged carbonyl and which containing
more than two metal atoms are called polynuclear carbonyls
which may be homonuclear e.g. Fe3(CO)12 or hetereonucear [e.g.
MnCo(CO)9, MnRe(CO)10].
GENERAL METHODS OF PREPARATION
(i) Direct Synthesis
(ii)By carbonylating metallic salts with CO in presence of
educing agent
(iii)Preparation of Mo(CO)6 and W(CO)6 from Fe(CO)5
(iv)Preparation of Fe2(CO)9, and Os2(CO)9 from Fe(CO)5
Direct Synthesis
Only Ni(CO)4 and Fe(CO)5 and Co2(CO)8 are normally obtained by the
action of CO on the finely divided metal at suitable tempreture and
pressure.
Ni 4CO R.T.,
100 atm
press.
Ni(CO) 4
Fe(CO)5 UV
-light
Fe 2 CO)9 CO
Os(CO)5 UV
-light
Os 2 CO)9 CO
GENERAL PROPERTIES
Physical properties
•Most carbonyls are volatile solids but Fe(CO)5, Ru(CO)5, Os(CO)5 and
Ni(CO)4 are liquids at ordinary temperature and quite inflammable.
Mo(CO)6 + Cl2
Mo(CO)4Cl2 + 2CO
Mn2(CO)10 + X2 (X=Br, I)
2Mn(CO)5X
Co2(CO)8 and Ni(CO)4 both get decomposed into metallic halides and CO when
treated with halogens. e.g.
Co2(CO)8 + 2X2
2CoX + 8CO
2
Ni(CO)4 + Br2
NiBr + 4CO
2
(iv) Action of NO
Many carbonyl react with nitric oxide to form metal carbonyl nitrosyls. e.g
Fe(CO)5 + 2 NO
Fe(CO) (NO) + 3CO
2 2
3Fe2(CO)9 +4NO
2Fe(CO) (NO) +Fe (CO) + Fe (CO) + 6CO
2 2 2 5 3 12
Fe3(CO)12 + 6NO
3Fe(CO)2(NO)2 + 6CO
Co2(CO)8 + 2NO
3Co(CO)3(NO) + 2CO
Ni(CO)4 + 4NO
Ni(NO)(NO2) + 4CO + N2O
(v) Action of H2
When Mn2(CO)10 and Co2(CO)8 react with H2, they are reduced to carbonyl
hydride, Mn(CO)5H and Co(CO)4H respectively.
Mn 2 (CO)10 H 2 200
atm. press.
2[Mn - (CO)5 H ]0
250 oC
Fe(CO)5
Fe 5CO
o
70 C, cool
3Fe 2 (CO)9 3Fe(CO)5 Fe 3 (CO)12
(in toluen e)
o
140 C, cool
Fe 3 (CO)12
3Fe 12CO
o
180 C
Ni(CO)
Ni 4CO
4
o
50 C
3Fe 2 (CO)9
2Fe3 (CO)12 3CO
(in toluen e)
Structure and nature of M-CO bonding in carbonyls
The lone paired of electron on carbon atom would expected to form strong
σ-dative bond due to electron density remain to the carbon nucleus.
In the type of M(CO)5 and M(CO)6 carbonyls dsp3 and d2sp3 hybrid orbital are
used for M←CO σ-bonds. In this bond formation, metal atom acts as electron
acceptor, while CO acts as electron donor.
Formation of dative π-bonds
This bond is formed as a result of overlapping of filled dπ orbitals or hybrid
dpπ orbitals of metal atom with low-lying empty pπ-orbitals on CO molecule.
i.e. M CO
i.e. Ni→CO π-bond in Ni(CO)4 form by overlap between filled dz2 or dx2-y2 on
Ni atom and empty π* molecular orbital on CO molecule.
M→CO π-bond form by overlapping with filled dxy, dyz or dxz orbital of M
with empty π* molecular orbital on CO molecule. Out of six CO, three are
linked by M←CO σ-bond and remaining three is linked by M←CO and
M→CO π-bond.
As M-CO donation increases, the M-C bond becomes stronger and the C=O
bond becomes weaker. Thus the multiple bonding would result in shorter M-C
bonds and longer C-O bonds as compared M-C single bonds and C=O triple
bonds respectively. The C-O bond lengths are rather insensitive to bond order,
the M-C bonds show appreciable shortening consistent with bonding concept.
Effective atomic number rule (EAN)
In the formation of M←CO bond, CO molecule electron pair to the metal atom.
Thus the metal atom is said to be have zero valency. The rule is state that
“After CO groups donated a certain number of electron pairs to the
zero valent metal atom through OC→M σ-bonding, the total number of
electron on metal atom including those gained from CO molecule
becomes equal to the atomic number of the next inert gas”.
EAN = z + 2Y = G
Where, z = total electrons of metal atom
Y = total electron donated by CO groups
In carbonyls, CO can donate two electrons at a time, so only even number of
transition metal can achieve the effective atomic number of next inert gas.
e.g. for Cr(CO)6,
EAN = z + 2Y = 24 + (2x6) = 36 = Ar
G = Effective atomic number of next inert gas
1) Mononuclear carbonyl having transition metal atom in even atomic number
Mo(CO)6 42 6 x 2 = 12 42 + 12 = 54 [Xe]
W(CO)6 74 6 x 2 = 12 74 + 12 = 86 [Rn]
Fe(CO)5 26 5 x 2 = 10 26 + 10 = 36 [Kr]
Ru(CO)5 44 5 x 2 = 10 44 + 10 = 54 [Xe]
Os(CO)5 76 5 x 2 = 10 76 + 10 = 86 [Rn]
V(CO)6: 23 + (2 x 6) = 35
Mn(CO)5: 25 + (2 x 5) = 35
Co(CO)4: 27 + (2 x 4) = 35
3) Polynuclear carbonyl:
Two ēs each of M-M bond present in these carbonyls are included in
calculating the ēs per metal atom.
Preparation:
(i) By the action of NaNO3 on Na4[Fe2+(CN)6]
Na4[Fe2+(CN)6] + NaNO2 + H2O → Na2[Fe2+(CN)5(NO+)] + 2NaOH +
NaCN